Method of inhibiting the growth of fungi by applying a complex of organic amine with a completely halogenated acetone

ABSTRACT

THE USE OF A CHEMICAL COMPLEX OF THE FOLLOWING FORMULA:   (X-CF2-CO-CF2-X&#39;&#39;)M (R1-NH-R2)N   WHEREIN R1 AND R2 ARE HYDROGEN: AN ALKYL RADICAL OF FROM 1 TO 18 CARBON ATOMS; AN ALKYL RADICAL OF FROM 1 TO 18 CARBON ATOMS; AN ALKYNL RADICAL OF FROM 1 TO 9 CARBON ATOMS; A NON-AROMATIC CARBOCYCLIC RADICAL OF FROM 5 TO 6 CARBON ATOMS; AN ARALKYL RADICAL WHEREIN THE ALKYL PORTION IS LOWER ALKYL AND THE ARYL PORTION IS A PHENYL OR NAPHTHYL RADICAL; PHENYL RADICAL; NAPHTHYL RADICAL; AN AMINO RADICAL; CYANO OR A HETEROCYCLIC RADICAL; AND WHEN TAKEN TOGETHER R1 AND R2 MAY FORM A HETEROCYCLIC RING SYSTEMS; IT BEING PROVIDED THAT THE AFORESAID RADICALS MAY HAVE ATTACHED THERETO THE FUNCTIONAL MOIETY; JALOGEN, -CN, -SCN, -COOR, -SO2NR2, -SOR, -SO3R,   -CONR2, -CONHR   -OH, -SH,-NR2,-NHR,-NH2, -OR, -SR,   -OC(O)R   CHO,   -CO-, -CH(-O-R)2   -NO2 AND -N=N, WHEREIN R CAN BE AN ORGANIC RADICAL OF THE TYPE ABOVE DEFINED FOR R1 AND R2; X AND Y&#39;&#39; ARE FLUORINE OR CHLORINE, AND N AND M ARE INTEGERS OF FROM 1 TO 3 WITH THE PROVISO THAT N AND M ARE IDENTICAL WHEN EQUAL TO UNITY AS A GUNGICIDE.

United States Patent @ifice 3,639,629 Patented Feb. 1, 1972 US. Cl. 424-325 Int. Cl. A01n 9/00 2 Claims ABSTRACT OF THE DISCLOSURE The use of a chemical complex of the following formula:

wherein R and R are hydrogen: an alkyl radical of from 1 to 18 carbon atoms; an alkyl radical of from 1 to 18 carbon atoms; an alkynyl radical of from 1 to 9 carbon atoms; a non-aromatic carbocyclic radical of from 5 to 6 carbon atoms; an aralkyl radical wherein the alkyl portion is lower alkyl and the aryl portion is a phenyl or naphthyl radical; phenyl radical; naphthyl radical; an amino radical; cyano or a heterocyclic radical; and when taken together R and R may form a heterocyclic ring system; it being provided that the aforesaid radicals may have attached thereto the functional moiety; halogen, CN, SCN, COOR, SO NR SOR, SO R,

-CONR CONHR OH, SH, NR NHR, NH OR, SR,

OC (0) R CH0,

0 OR ll -0-, -CH

NO and N=N, wherein R can be an organic radical of the type above defined for R and R X and X are fluorine or chlorine, and n and m are integers of from 1 to 3 with the proviso that n and m are identical when equal to unity as a gungicide.

This invention relates to the control of microorganisms such as fungi and the like. More particularly, the invention pertains to the control of fungi by means of systemlcally working fungicidal compositions containing as their active component a complex of an organic amine with a completely halogenated acetone. This is a divisional application of application Ser. No. 802,740 filed Feb. 17, 1969 which is a continuation application of application Ser. No. 308,362 filed Sept. 13, 1963, now abandoned which is a continuation-in-part of application Ser. No. 221,456 filed Sept. 5, 1962, now abandoned.

In accordance with the present invention, it has been discovered that certain completely halogenated acetones having at least two fluorine atoms per methyl group and in which the two remaining halogens are fluorine or chlorine are capable of forming chemical complexes with relatively basic organic amines thereby engendering a family of chemical adducts which have proved to be unusually potent as systemic fungicides, and the provision of such compleXes and a method of preparing them constitutes the principal object of the present invention. It is also an im portant object of the invention to provide fungicidal com positions containing at least one of the aforesaid complexes. Other objects and purposes will become manifest subsequently.

The systemic fungicides of the present invention can be represented by the following general formula:

wherein R and R; can be hydrogen, an alkyl radical of from 1 to 18 carbon atoms, an alkenyl radical of from 1 to 18 carbon atoms, an alkynyl radical of from 1 to 9 carbon atoms, a non-aromatic carbocyclic radical of from 5 to 6 carbon atoms, an aralkyl radical wherein the alkyl portion is a lower alkyl and the aryl portion is a phenyl or naphthyl radical, an aromatic hydrocarbon radical such as a phenyl or naphthyl radical, cyano, an amino radical which may be substituted by lower alkyl and aryl radicals having from 1 to 2 aromatic rings and a heterocyclic radical, and taken together R and R may form a heterocyclic ring system as exemplified by pyrrole, pyrrolidine, imidazole, imidazoline, imidazolidine, piperazine, morpholine, isoxazine, dioxazole, tetrazole, and the like, it being provided that the aforesaid radicals may have attached thereto such functional moieties as halogen, e.g. chlorine, bromine or fluorine, CN, SCN, COOR, -SO NR SO R, SOR, SO R, CONR NO and NEN, wherein R can be a hydrocarbon radical of the type defined for R and R X and X represent a halogen selected from the class consisting of fluorine and chlorine, and n and m are integers of from 1 to 3, it being understood that when n and m are identical they are equal to unity.

4 Specific values which may be assigned to R and R of Heterocyclic radicals the above given formula are set forth in the following list: 2 pyridy1 diazinyl 3-pyridyl Z-thiazolidyl l Alkyl radlca S 5 OXaZOlyl 4,S-dimethyl-Z-thiazolidyl methyl Z-methoxyethyl thiazolyl 2-pyrimidyl ethyl 3-ethoxypropyl Plf y 4-phenyl-2-oxazolyl n-propyl 3-nitropropyl tnazolyl py f yl isopropyl formylmethyl tetraolyl benzimidazolyl n-pentyl 3-hydroxy-2-oxo-propyl 1O oxadlflzolyl PY Y isopentyl ethoxycarbonylethyl ofiatrlalolyl B" P 'hOll1laZOl l isobutyl 2-acetomidoethyl dlalolyl triaz nyl tert.-butyl 2N,N-dimethylacetomidofurfuryl OXaZIHYI .mhexyl f h 1 In general, the compounds as contemplated herein are lsohexyl t locyanaltoet y prepared by chemically combinig in molar proportions as nmonyl phenethy 1 above shown in the general formula the halogenated acen'decyl 3'ethylmercaptopropy tone and a basic amine component of the formula bromoethyl Z-fiuoroethyl chloroethyl 2-cyanoethyl R1 Z-nitrobutyl 2-butoxypropyl N41: Z-dimethylaminoethyl 2-chloro-2-nitropropy1 Z-diethylaminoethyl 2,3-dibromopropyl H z3-dlhydroxypropyl 333'mchloro'z-mtmpmpyl wherein R and R have the values as previously desigz'pmpoxyethyl nated. The reaction is conveniently carried out in the presence of a normally liquid organic solvent, and in this connection reference is made to the lower ketones as exemplified by acetone, methylethylketone, and the like,

Ethylenically unsaturated radicals 5-hex n l figi n alkyl cyanides, e.g. acetonitrile, and saturated aliphatic ethallyl Z-methyl-l-hexenyl and aromatic hydrocarbons as well as their normally 1 buteny1 3 ethyl l hexenyl liquid chlorinated derivatives such as methylene dichlo- 4,441 th I ride, carbon tetrachloride, chloroform, ethylene dichlo- 2butenyl la y exeny ride, chlorobenzene, m-dichlorobenzene, etc. With the gil gl gilpb l 25223 more reactive amines, usually those of fairly high basicity, 2 1 3 1 4,4 dimethyl l octenyl the reaction with the fluoroacetone can be rather v gorous p m l 4 1 and commonly occurs spontaneously on br nging to- 2 1 1 octeny1 gether the reactants, necessitating external cooling means. 3-pentenyl 2-octenyl On the other han d, the less reactive amines may require 4 1 3 0cteny1 exterrial heating in order to complete formation of the comp ex. igifigi gigfiji It is to be understood that the term relatively basic 2-ethyl-4-pentenyl 4,4-dimethyl-2-octen 1 ne refers to those organic amines WhlCh form stable salts with strong acids as exemplified by sulfuric acid,

33 d1methy1-1 penteny1 Lnonenyl hydrochloric acid, hydrobromic acid, perchloric acid, and

23225} ig gf 4r thelike. By stable amine salts is meant those which can 3 hexenyl smonenyl 0 1solated and are stable under normal or ambient con- 1 ions. 4-hexenyl 2 decenyl Although the amine-halogenated complexes of the Acetvlenicany unsaturated radicals invention exert an overall influence on the metabolism of a wide spectrum of plant life, they are particularly effec- 1 Pmpyny1 7 1 tive in controlling the growth of fungi and other similar 2 propyny1 (propargyl) 2 1 1 3 types of n n' croorganisms. In general, we have found that l hexynyl 1 b -2 1 the parasitic undifferentiated microorganisms are to a 3-hexynyl 3,5-dimethyl-1-hexyny1 considerable degree more susceptible to the toxicants than boats/[W1 the highly organized members of the plant kingdom. The aforesaid property is especially useful where it is desired Non-aromatic carbocyclic radicals to protect a valuable food crop against infection from attacking plant parasites. For instance, the compounds cyclopentyl 2-cyclohexeny1 can be safely applied to bean plants to protect them against cyclohexyl 3-cyclohexenyl rust and mildew. l-cyclopentenyl 2-(3-cyclohexenyl)ethyl-3- As previously pointed out, the complexes of the inven- Z-cyclopentenyl vinylcyclohexyl tion are systemic fungicides and this unexpected finding 3-cyclopentenyl 4-ethyl-1-cyclohexenyl greatly increases their usefulness and versatility. As those 4-vinylcyclohexyl 4-isopropyl-2-cyclohexenyl skilled in the art are aware, a systemic fungicide is taken l-cyclohexenyl up internally by the plant to which it is applied and lodges in the plant tissues while still retaining toxicological Phenyl and naphthyl radicals properties. Obviously, systemic toxicants are not subject to weathering since they are confined within the interstices P y 2,4-dih10T0PheHY1 of the plant tissues which are thus internally immunized p y y against the attack of harmful microorganisms such as 4-chlorophenyl 4-chloromethylpheny1 fungi, mold r t d th lik 4-fl ph nyl l-naphthyl Preparations suitable for fungicidal applications may 4-hydroxyphenyl 4-chlor-o-1-naphthyl be prepared in the form of dusts or sprays. For instance, dichlorophenyl l-methyl-Z-naphthyl a dust is prepared by intimately blending the halogenated 4-cyanopheny1 Z-naphthyl acetone-amine complex with a finely divided solid carrier 4-diethylaminopheny], 4-ethoxyphenyl of which talc, diatomaceous earth, pyrophyllite, hydrated silica, clay and bentonite are typical examples. The active component'normally comprises about 1 to 15% of the total mixture. Moreover, it is a common practice to employ wetting agents to facilitate dispersing the active material in the event the dusts are added to water. Typically, a wettable powder may comprise 20 to 50% of the complex, 45 to 75% of one of the aforementioned finely divided solids, and 1 to 5% of a wetting agent. The aforesaid mixtures can be further diluted if desired. Exemplary wetting agents are the sodium alkylbenzenesnlfonates, sodium dodecyl sulfate, and the nonionic polyethers as exemplified by the alkylphenoxy-polyethoxyethanols. In use, the wettable powder is stirred up in water and the resultant liquid sprayed on plants for protection against fungus diseases. Another common procedure for incorporating the toxicants of the invention in a form suitable for application to plants consists of dissolving the toxicant in an organic solvent such as xylene, toluene, ethylenedichloride followed by emulsifying the resulting solution in water in the presence of a dispersing agent. The solvent solution can also be applied directly.

solution containing the compound undergoing evaluation was diluted until the concentration was 50 parts per million and the resultant diluted solution then placed in small tubes. A pinto bean plant was inserted in each tube using a cotton plug to support the seedling and also to retard evaporation. After 48 hours, two plants were inoculated with bean rust. Comparison between the treated and untreated plants was then made and the results evaluated. In these tests, the compound of Example 11 gave 100% control at a concentration of 1 part per million which, it will be noted, was the lowest concentration tested. Manfestly, this compound exhibits an unusually high degree of activity as a systemic fungicidal agent.

For specific instructions and directions for preparing the aforementioned complexes, reference is now made to the following examples which are inserted only for the purpose of illustrating the invention. It will be appreciated by those skilled in the art to which the invention pertains that various modifications and ramifications can be effected without departing from the spirit and scope thereof.

EXAMPLE 1 20.0 g. of sym. dichlorotetrafiuoroacetone was diluted with 50 ml. of methylenedichloride and to the resulting solution as added gradually 9.3 g. of aniline. An exothermic reaction ensued, the result of which was to cause refluxing of the reaction. Following the addition of the amine, the reactionmixture was distilled under reduced pressure in order to remove all volatile products. There was obtained 19.5 g. of a slightly yellow residual oil which gradually solidified on cooling. The crude product was trituratedwith about 30 ml. of hexane, from which was obtained 15 g. of a white solid melting at 38 C. Analytical data and molecular weight determination were in consonance with the above depicted structure.

EXAMPLE 2 The procedure of Example 1 was again carried out but using equal molar proportions of sym. dichlorotetrafluoroacetone and m-am-inophenol. In general, the results were in consonance with those of the first example. After purification by crystallization from ether, there was obtained a light tan solid, the chemical analysis of which corresponded to the above depicted structure. This is an example of a complex wherein the molar ratio of reactants is EXAlePLE 3 C4110 C F NCH2CH CHzNH [C 0 4 0 I. C Fa z 4.8 g. of di-nbutylamino propylamine was dissolved in acetone and to the resulting solution was added 11.0 g. of hexafluoroacetone. After the initially exothermic reaction had subsided, the reaction mixture was subjected to reduced pressure and the volatile components distilled off. The desired product was obtained in the form of a yellow, viscous, oily residue which solidified on standing to a light yellow solid. The yield of product was 13 g.; M.P. 124- 126 C.

EXAMPLE 4 Chloropentafluoroacetone was dissolved into a mixture consisting of 4.8 g. furfurylamine and 30 ml. of methylene chloride, the introduction being continued until 5.5 g. of the halogenated acetone has been absorbed. After removal of the volatile components from the reaction mixture, there was obtained 10.0 g. of a residual yellow oil having an N of 1.4418.

7.0 g. of sym. dichlorotetrafluoroacetone was slowly added to a mixture of 9.2 g. of sulfamethazine suspended in 20 ml. of acetonitrile. There resulted an exothermic reaction with concomitant dissolution of the amine adduct. After the reaction was completed, as indicated by the falling temperature, the product precipitated as a voluminous, light yellow solid. The product was isolated by filtration and after drying amounted to 14.0 g. and decomposed at 120-125 C.

EXAMPLE 6 \N NH2 CCIF2 4.8 g. of 2-amino-4-picoline was suspended in 40 ml. of methylene chloride and to the resulting mixture was added 10.0 g. of sym. dichlorotetrafiuoroacetone. After the addition, the picoline underwent dissolution and after removal of the volatile components by distillation, there was obtained 14.7 g. of a white solid which melted at 117 C.

EXAMPLE 7 CH3 0 cm, N: 0 a o NH o 01F:

CH=CH 4.1 g. of Z-methyl imidazole was suspended in 30 ml. of methylene dichloride to which was added 10.0 g. of sym. dichlorotetrafluoroacetone. There occurred immediately a rather mild exothermic reaction followed by simultaneous separation of the addition product. Isolation was effected by filtering off the white solid; its M.P. was 96100 C.

EXAMPLE 9 3.25 g. (0.025 M) diethylaminopropylamine was mixed with ml. of methylene dichloride. To this solution was added 5.0 g. 0.025 M) of sym. dichlorotetrafluoroacetone. After the initially mild exothermic reaction had subsided, the mixture was allowed to cool to room temperature followed by the addition of 20 ml. of acetone and 4.1 g. (0.025 M) of hexafluoroacetone. The temperature of the reaction rose to about C. and then gradually dropped back to room temperature. The reaction mixture was subjected to reduced pressure for removal of excess solvent and volatile components, after which there remained 13.0 g. of a residual viscous, yellow oil having an N of 1.4154. The chemical and instrumental analyses of the product was in consonance with the above depicted structure and it is an example of an amine halogenated acetone complex in which two diiferent halogenated acetone adducts are combined in the same complex.

Using the procedure as set forth in the previous examples, complexes of various halogenated acetones were prepared from the amines listed below.

Ratio amine Halogenated halogenated Example N0.

Amine acetone acetone Characterization 17 .11.. GioHmNHz 4FK 18 IFK (|]H2 11TH CH CHg-NHz 2O C2H5 4FK Cal-I5 NHz OH NHz HO- NH2 032 /NH CH CH 28 CHr-CHZ 4FK NH CH -CH 29 Cl 4FK White solid, M.P. 56 C.

Brown oil, 1zn=1.4213. Dark yellow oil, nD'- =1.4345.

Orange oil, n 25=1.4909.

White solid, M.P. C.

.. Yellow 011, 1m =1.4260.

2:1 Straw yellow oil, n =115265.

2:1 Brown oil, nn=1.5225.

2:1 White solid, M.P. 48 C.

1:1 Grey solid, M.P. 6369 G.

2:1 Grey solid, decomposes above 106 0.

1:1 Yellow solid, M.P. 110 C.

Orange oil, np"=1.4478.

2:1 Yellow oil 'n =1.4460.

211 Yellow oil, nn=l.5496.

. Y Ratio amine: alogenated halogenated Examp e Am e, .7 e eweql 77 999W? Qh Q QW MQK 51 Ethylene lnimQU-L 1:1 White solid, M.P. 107 c, 52 B-aminod,2,4-triazoie.-. 1:1 White solid, MZP. 70 C.

IfiI (DH-NH; N N.

53 2,6-dimethy1piperidine 4FK 1:1 Brown oil,1l =1.4313. smog-0H3 OH: NH

omen-0H3 V 54 4FK 1:1 Light brown solid, M.P'." i7 c.

NOz- NHNH;

55 NHzCHzCHzO 4FK White solid,

65111111111111: 3-aminomethylpyridine 4FK CH NH1 66 6-amino-2,4-butidine 4FK 67 2-amino-3-pieoline 4FK 68- 2-amino-5-nittopyridine. 4FK 69 2,6diaminopyricline 4FK 70 Dimetilylaminopropylamine 4FK 71 Diethylaminopropylamine 4FK 72 CH3 4FK NNH2 73 C4H9NH-CH2CH2OH 4FK 74 Z-aminopyrimidine 4FK 15 Triaminopyrimidine-- 4FK 76. Benzimidazole 4FK 77 0 4FK 78 Dihydro-2,2,4,6-tetramethyl pyridine 4FK C CH:

\(IJH ([?CH: C\ /CH N H CH;

79 CH3NHCH2CH2CN. 4FK 80 Methoxypropyiamine..- 4FK 81 OHa 4FK CHO-CHzCH2C 2N 2 0 3 II I 4FK 82 CH2=CCOCH2CH2NHCCH:;

CH3 CHI 83 Di-(u-butylamino)propylamine 4FK 84 do l. 4FK 85 Melamine 41 K 86 N-(-y-ominopropyl)morpholine 4FK 87 3-chloro-4-benzamido-fi-methylaniline 41 K /CHNH-GH1CH2CN 4FK M.P. White solid, M.P.

Grey solid, M.P. 94C.: White solid, M.P. 118 C.

White solid, M.P.'142 C. Slightly yellow solid, M.P. 98 0. Yellow solid, M.P. 70 0.

Grey solid, M.P. 96 C.

Viscous amber oil, 7m =l.4508.

White solid, M.P. White solid, M.P. White solid, M.P. 8 C. White solid, M.P. 6 C. White solid, M.P. 142 C. Red liquid, 11.11 =1.4592.

Yellow liquid, nn=1.4370. Water clear oil, n1 =-1.-4260.

Yellow liquid, 1m=1.4300.

Viscous yellow oil, 'nn =1 4532.

,Orange oil, 'rm=1.4475.

Orange oil, nD =1.4337. V White solid, M.P. 65 0-. Yellow oil, nD =1.471 0. White solid, M.P. 102 0.

Ratio amine: Halogenated halogenated Example No. Amine acetone acetone Characterization 'CHzCIIgCN 1:1 Viscous yellow oil, nD =1.4594.

89 NH 4FK CHzCHaCN 90 Imidazole 4FK 1:1 White solid, M.P. 102 0. 91 2-phenaoylmeroapto-2-imidazoline 4FK 1:1 Yellow solid, M.P. 122 C.

0 N ll C-CH2SC CH2 N H-C H2 92 Hexahydro-l,3,5-tripheny1-s-triazine 4FK 1:3 Red oil, nD =1.5110. 93 Casein 4FK Yellow oil, raw- 1.4283. 94 2-0yanimino-4-methylpyrimidine. 4FK 1:2 Yellow solid, M.P. 197 C.

N NCNH(I) C-CH;

95 2-amino-4-hydroxy-dmethyl-pyrimidine 4FK 1:1 syrupy product, m =1:4430. 96 2-amino-ichloro-7-methyl pyrimidine. 4FK 1:1 White solid, M.P. C. 97 Funurylaxnine 4FK 1:1 Colorless oil, 111;:13524. 98 1,3-diphenyltriazene 4FK 1:1 Dark brown oil.

Q K j 99 EtaN-salt of 4FK 1:1 Gel.

- 4FK 1:1 Yellow product, 71D =1.5017. HOOC-CH2S ,NH2

100 Phenylhydrazine AFK 1:1 White solid, M.P. 59C. 101 2-benzylamino-4,5-dihydro imidazole 4FK 1:1 Yellow solid, M.P. 131C.

N-CH2 CHzNHO 11.1 1 WW, .NH, CH2 .01..

102 Phenylazoanlline 411; 1:1 Dark oil.

103 Sulfapyridine. iFK 1:2 White solid.

| I NH-SOz-,-NH2 V N 104 Suliethiazolm. 4FK 1:3 White Solid, M.P. 175C. .1 --l N L J NH-SOFQNI-n 105 Sulfathiazolfi. 4FK 1:1 White solid (decomposes over 100 0.). 10 Suliapyridine 4FK 1:1 White solid (decomposes gradually on heating). 107. Suliaguanidin 4FK 1:1 Glassy semisolid. 108 Glycine ethyl este iFK 1:1 Yellow oil, 1m"=1.4322.

C2H5'OC-CHg-NH 109 2-amino-4-chloro-6-methyl-pyrimidine; 6FK 121 White solid, M.P. 64 C.

Z-cyanimino-i-methyl-pyrimidine 6FK 1:1 Viscous yellow oil. t-Butylan ino-methacrylate 1:1 Rubber-like polymerizatel 112 "-CHa' I Q N-NHz eFK 1:1 Colorless 011, =13340i CH3 I 113 3-amino'5-pyraz01one 4FK 1:2 Red viscous oil, nn =1.4578.

IIIH: (|JCH2 N-N Q-aminoE-chloropyridine 4FK 1:1 White 501111, Mfr. 76 0.

amino-kphenyl-2-pyrazolin-5-one- 4FK 1:1 White solid ,M.P. 95-110" 0. i diarnirioa zolgenzen 112 Red viscous oil. 1-methylpiperezine; 1:1 Do.

Ratio amine: Halogenated halogenated Example No; Amine acetone acetone Characterization 2-methylpiperazine .t 4FK 1:2 Yellow oil, nr =1.4538. O-phenylenediamine 4FK 1:1 Tan solid, M.P. 85 C.

4-nitrophenylenediamine 4FK 1:2 Brown 011, nD =l.435. CH;NH-NH 4FK 1:2 Clear yellow oil, 1m =1.42l0.

122 N 4FK 1:1 White solid (decomposes on heating gradually, melts at 250 0.). N

123 Sulfanllamide 4FK 1:1 White solid, MP. 83 C:

124. w. N-sullanilylbenzamide 4FK 1:1 White solid, MP. 17580 O:

126 Ethylenediamine 4FK; GFK 1:2 Viscous oil, n =1.4005. 127 Phenylacetoguanamine 4FK 1:1 White solid, MP. 88 C.

N w W V NH:

128 Thiurat 4FK 122 Red viscous oil, n =1A68L ll C-S\ 8 NIL-("3 CFaCl CF: /CF;

4FK= C=0 6FK= C=O 6FK= C=0 CFzCl; C2301; CFa.

The systemic funglcldal activity of the above described 45 TABLE-C011flH11ed addition complexes is mdrcated m the table below. Test tube System Foliage bean rust (p.p.m.) .p.m.) TABLE 1,000 500 100 Rust MlldBW F n b t Test tube sysjtemle 50 50 0 age ean rus p.p.m. .p.m. Example p 44 100 1' *50 50 No. 1,000 500 100 Rust Mildew 45 100 100 l '50 12 100 100 5 50 5 50 52 100 100 100 5 50 1 46 100 100 100 1 10 50 48 100 100 100 5 as 100 100 100 a 25 50 54 100 100 100 5 50 50 52 100 100 100 l 50 50 51 100 100 5 50 50 69 100 100 50 25 NOTE.++++=90% control; control; +++=75% control; +=l0% control; =lowest concentration (ppm) tested to date; 50 inhibition of some degree at p.p.m. indicated.

25 We claim: :23 1. A method of mhlbltmg the growth of fung1 which 50 comprises applying thereto a fungicidally efiective amount 2? of a chemical complex of the formula:

32 wherein R and R are selected from the class consisting 50 of hydrogen, an alkyl radical of from 1 to 18 carbon 50 atoms, an alkenyl radical of from 1 to 18 carbon atoms 50 selected ifirom the group consisting of cyclopentyl, cyclohexyl, l-cyclopentenyl, 2-cyclopentenyl, 3-cyc1opentenyl, 10 4 vinylcyclohexyl, 1 cyclohexenyl, Z-cyclohexenyl, 3- cyclohexenyl, 2(3 n cyclohexenyn-ethyl 3 vinylcyclo- 17 hexyl, 4 ethyl 1 cyclohexenyl and 4-isopropyl-2-cyclohexenyl, an alkynyl radical of from 1 to 9 carbon atoms, a non-aromatic carbocyclic radical of from 5 to 6 carbon atoms, an aralkyl radical wherein the alkyl portion is lower alkyl and the aryl portion is an unsubstituted phenyl or naphthyl radical, an aromatic hydrocarbon radical selected from the class consisting of unsubstituted phenyl and naphthyl radicals, an amino radical, cyano, and a heterocyclic radical selected from the group consisting of 2-pyridyl, 3-pyridyl, oxazolyl, thiazolyl, pyrrolyl, triazolyl, tetraazolyl, oxadiazolyl, oxatriazolyl, diazolyl, furturyl, diazinyl, 2 thiazolidyl, 4,S-dimethyl-Z-triazolidyl, 2-pyrimidyl, 4 phenyl-2-oxazolyl, pyranyl, benzimidazolyl, pyrazolonyl, B-naphthothiazolyl, triazinyl and oxazinyl, and when taken together R and R may form a heterocyclic ring system selected from the group consisting of pyrrole, pyrrolidine, imidazole, imidazoline, imidazolidine, piperazine, morpholine, isorazine, dioxazole, tetrazole, 3- azo-bicyclo-[3,2,2]-nonane, ethyleneimine, 2,6-dimethylpiperidine, benzotriazol, benzimidazole, it being provided that the aforesaid radicals may have attached thereto a functional moiety selected from the class consisting of halogen, ON, SCN, COOR, SO NR SOR, SO R, CONR CONHR, OH, SH, NR NHR, NH OR, SR, --OC(O)R,

0 OR ll 0, OHO, OH

NO and N=N, wherein R can be an organic radical of the type above defined for R and R X and X are chlorine, and n and m are integers of from 1 to 3 with the proviso that n and m are identical when equal to unity.

2. The method of claim 1 in which X is chlorine, X is chlorine, m is the integer one, R is hydrogen, R is hydrogen and rt is the integer one.

References Cited UNITED STATES PATENTS 2,853,524 9/1958 Miller et a1. 260-593 3,226,439 12/1965 Middleton et a1. 260'566 3,323,984 6/1967 Szabo et a1. 260593 OTHER REFERENCES Chemical Abstracts, vol. 54, cols. 20962-20963 (1960). Chemical Abstracts, vol. 63, col. 482 (196 5). Middleton et al., J. Org. Chem. vol. 30, pp. 1398-1402 (1965).

JEROME D. GOLDBERG, Primary Examiner D. M. STEPHENS, Assistant Examiner US. Cl. X.R. 

